Herbicidal 4-trifluoromethyl-4&#39;-nitrodiphenyl ethers

ABSTRACT

COMPOUNDS OF THE FORMULA   1-(O2N-),2-Z,4-((2-X,4-(F3C-),6-Y-PHENYL)-O-)BENZENE   WHEREIN X IS A HYDROGEN ATOM, A HALOGEN ATOM, A TRIHALOMETHYL GROUP, AN ALKYL GROUP, OR A CYANO GROUP, Y IS A HYDROGEN ATOM, A HALOGEN ATOM, OR A TRIHALOMETHYL GROUP, AND Z IS AN ALKOXY GROUP, AN ALKOXYALKOXY GROUP, A HYDROXYALKOXY GROUP, AN ALKYL GROUP, A HALOGEN ATOM, AN ALKYLAMINO GROUP, A DIALKYLAMINO GROUP, AN ALKYLTHIO GROUP, A CARBOXY GROUP, A CARBALKOXY GROUP, A CARBOXYALKYL GROUP, A CARBALKOXYALKOXY GROUP, A CARBOXYALKYL GROUP, A CARBALKOXYALKLY GROUP, A DIALKYUREIDO GROUP, ANY ALKANOYLAMINO GROUP, OR A CARBALKOXYAMINO GROUP, AND COMPOSITIONS CONTAINING THESE COMPOUNDS EXHIBIT HERBICIDAL ACTIVITY.

United States Patent 3,798,276 RBICIDAL 4-TRIFLUOROMETHYL 4'-NITRODIPHENYL ETHERS Horst 0. Bayer, 186 Red Rose Drive, Levittown, Pa. 19056; Colin Swithenbank, 1710 W. Rock --Road, Perkasie, Pa. 18944; and Roy Y. Yih, 73 Townview Drive, Doylestown, Pa. 18901 No Drawing. Filed Mar. 14, 1972, Ser. No. 234,651 Int. Cl. C07c 43/28 US. Cl. 260-612 R 6 Claims ABSTRACT OF THE DISCLOSURE Compounds of the formula wherein Y X is a hydrogen atom, a halogen atom, a trihalomethyl group, an alkyl group, or a cyano group, p Y is a hydrogen atom, a halogen atom, or a trihalomethyl q n d Z -is an alkoxy group, an alkoxyalkoxy group, a hydroxyalkoxy group, an alkyl group, a halogen atom, an alkylamino group, a dialkylamino group, an alkylthio .group,a carboxy group, a carbalkoxy group, a car- "boxyalkyl group, a carbalkoxyalkoxy group, a carboxy} alkyl group, a carbalkoxyalkyl group, a dialkylureido group, an alkanoylamino group, or a carbalkoxyamino p; v and compositions containing these compounds exhibit herbicidal activity. L

; THE DISCLOSURE This invention relates to novel compounds which show activity as herbicides, to novel herbicidal compositions which contain these compounds, and to new methods of controlling weeds with these herbicidal compositions.

Certain diphenyl ethers have been shown to be effective weed control agents. Howeverythe herbicidal 'efiectivene'ss of a given diphenyl ether cannot be predicted-from an examination of the substituent groups attached to the phenyl rings in the ether, and often quite closely related compounds will have quite different weed control abilities. Various diphenyl ethers may have overlapping or com plementary areas of activity or selectivity, and can thus be useful in combination-to control a variety-of weeds upon application of a single composition. Furthermore, the

diphenyl ethers heretofore: disclosed as herbicides are not completely efiective. An ideal herbicide should give'selective'weed control, over the full'growingseason, with a single administration at low rates of application. It should be able to control all common weedsby killing them as the seed, the germinating seed, the seedling, and thegrowing plant. At the same time, the herbicide should not be phytotoxic to the crops to which it is applied and should decompose or otherwise be dissipated so as not to poison the soil permanently. The known diphenyl ether herbicides fall short of these ideals, and it would thus be desirable ice to have new herbicides which show even more selective control of undesirable plants among desirable crop plants or which complement the known diphenyl ethers in activity.

In accordane with the present invention, there is provided a new class of novel diphenyl ethers having the formula wherein X is a hydrogen atom, a halogen atom, preferably a fluorine atom or a chlorine atom, a trihalomethlgroup, preferably a ,trifluoromethyl group, a (C -C alkyl group, preferably a methyl group or a cyano group,

Y is a hydrogen atom, a halogen atom, prefreably a fluorine atom or a chlorine atom, or a trihalomethyl group, preferably a trifluoromethyl group, and

Z is an alkoxy group, preferably having 1 to 6 carbon atoms, and most preferably 1 to 4 carbon atoms, an alkyl group, preferably having -1 to 4 carbon atoms, an alkoxyalkoxy group, preferably having 1 to 4 carbon atoms in each of the alkyl moieties, a hydroxyalkoxy group, preferably having 1 to 4 carbon atoms, a halogen atom, preferably a chlorine atom or a fluorine atom, an alkylamino group, preferably having 1 to 4 carbon atoms, a dialkylamino group, preferably having 1 to 4 carbon atoms, an alkylthio group, preferably having 1 to 4 carbon atoms, a carboxy group, a carbalkoxy group, -CO R, preferably having 1 to 4 carbon atoms in the alkoxy moiety, a carboxyalkoxy group, -OR' CO H, preferably having up to 4 carbon atoms, a carbalkoxyalkoxy group, ORCO R, preferably having up to 4 carbon atoms, a carboxyalkyl group, R'CO H, preferably having up to 4 carbon atoms, a carbalkoxyalkyl group, R'CO R preferably having up ,to 4 carbon atoms, an N,N dialkylureido group, -NHCONR preferably having 1 to 4 carbon atoms in each of the alkyl groups, an alkanoylamido group, NHCOR, preferably having up to 4 carbon atoms, or a ca'rbalkoxy amino group, --NHC0 R, preferably having up to 4 car-hon atoms.

In the above definitions of the Z substituent, R represents an alkyl group, and R represents a divalent alkylene group. The alkyl or alkylene portion of the alkyl-containing X and Z substituents can have either a straightor branched-chain or a cyclic spatial configuration. These novel compounds have been found to show unexpected activity as weed control agents. In a preferred embodiment of the invention, X is a halogen atom or a cyano group, Y

2 -chloro-a,a,a-trifluoro-p-toly1-4-nitro-m-tolyl ether,

2-bromo-a,a,u-trifluoro-p-tolyl-3 -butyl-4-nitropheny1 ,ether,

2,u,a,u-tetrafluoro-p-tolyl-4-nitro-3 -n-propoxyphenyl ether,

.3 z-chloro da, ot-tetrafluoro-p-tolylfl methylthio-4- v,

nitrophenyl ether, 2-chloro-a,a,a-trifiuoro-p-tolyl-3-methoxy-4-nitropheny1 ether,

2-chloro-a,a,a-trifluoro-p-tolyl-3-ethoxy-4-nitrodiphenyl ether, a,a,a-trifiuoro-2-iodo-p-tolyl-3-ethoxy-4-nitrophenyl ether, 2,6- dichloro-a,a,u-trifluoro-p-tolyl-4-nitro-3 -n-propoxyphenyl ether, o e,a,a,ot',a'-hexafluoro-2,4-xylyl-3-n-butoxy-4-nitrophenyl ether, 2-cyano-a,a,a-trifluoro-p-tolyl-3-ethoxy-4-nitrophenyl ether, I 2-chloro-6-cyano-a,a,a-trifluoro-p-tolyl-4-nitro-3-npropoxyphenyl ether, 2cyano-u,a,a-trifluoro-p-tolyl-3-carboxy-4-nitrophenyl ether, 2,6-dibromo-a,a,a-trifluoro-p-tolyl-3-methoxymethoxy- 4-nitrophenyl ether, 2-chloro-a,a,a-trifluoro-p-tolyl-3- (Z-hydroxy) ethxy-4- nitrophenyl ether, 2,a,a,a-tetrafiuoro-p-tolyl-4-nitro-3-n-propylaminophenyl ether, 2-chloro-a,u,m-trifluoro-p-tolyl-3-dimethylamino-4- nitrophenyl ether, 2-cyano-a,u,a-trifiuoro-p-tolyl-3-carbethoxy-4nitrophenyl ether, 2,6-dlChlOIO-OL,OL,d-tIlfluOI'O-P-lOlyl-3-CaI'b6thOXy-4- nitrophenyl ether, 2-ethyl-a,a,u-trifiuoro-p-tolyl-3-(2-carboxy)ethoxy-4- nitrophenyl ether, mega,a',a,u'-hexafiuoro-2,4-xylyl-3-carbethoxymethyl- 4-nitrophenyl ether, 2-cyano-u,a,a-trifiuoro-p-tolyl-3- (2-carboxy) propyl-4- nitrophenyl ether, 2,a,u,a-tetrafluoro-p-tolyl-3-carbethoxymethoxy-4- nitrophenyl ether, 2-chloro-a,ot,a-trifluoro-p-tolyl-3- (N,N-diethylureido) 4-nitrophenyl ether, 2-chloro-6-cyano-a,a,a-trifiuoro-p-tolyl-3-acetamido-4- I nitrophenyl ether, 2-chloro-a,a,a-trifluoro-p-tolyl-Ii-carbethoxyamino-4- nitrophenyl ether, Z-chlorwa,a,a-trifiuoro-p-tolyl-3-chloro-4-nitrophenyl ether,

and the like.

..Under.,some conditions,..tl1e..diphenyl. ethers. of. thejn- The novel diphenyl ethers of the invention are useful both as preemergence and as postemergence herbicides. Preemergence herbicides are ordinarily used to treat the soil in which the desired crop is to be planted by application either before seeding, during seeding, or, as in most applications, after seeding and before the crop invention can be advantageously employed are, for example, cotton, soybeans, peanuts, beans, peas, carrots, corn, and other cereal crops. I

The diphenyl ethers of the invention are useful for controlling weeds in rice crops. When used in trans-. planted rice crops, the ethers can be applied either. pre: emergence or postemergence to the weeds-that is, they can be applied to the transplanted rice plants and their growth medium either before the weed plants have emerged or while they are in their early stages of growth, The ethers can be applied to the growth medium either before or after the rice has been transplantedto that medium.

The diphenyl ethers of the invention can'be applied in any amount which will give the required control of weeds. A preferred rate of application of the herbicides of the invention is from about 0.1 to about 12 poundsof the diphenyl ether per acre.

vention may be advantageously incorporated into the soil or other growth medium prior to planting a crop. This incorporation can be carried out by any convenient means, including by simplemixing with the soil, by applying the ,diphenyl ether to the surface of the. soil and then disking or dragging into the soil to the desired depth, or by employing a liquid carrier to accomplish the necessary penetration and impregnation.

Adiphenyl-ether of the invention can be applied to the growth medium or to" plants to be treated either by itself or, as is generally done, as a component in a herbicidal composition or formulation which also comprises an agronomically acceptable carrier. By agronomically acceptable carrier is meant any substance which can be used to dissolve, disperse; or diffuse a herbicidal compound in the composition without impairing the effectiveness of the herbicidal compound and which by itself has no detrimental effect on the soil, equipment, crops, or agronomic environment. Mixtures of the diphenyl ethers of the invention may also be used in any of these herbicidal formulations. The herbicidal compositions of the invention can be either solid or liquid formulations or solutions. For example, the diphenyl ethers can be formulated as wettable powders, emulsifiable concentrates, dusts, granular formulations, aerosols, or flowable emulsion concentrates. In such formulations, the compounds are extended with a liquid or solid carrier and, when desired, suitable surfactants are incorporated.

It is usually desirable, particularly in postemergence applications, to include adjuvants, such as wetting agents, spreading agents, dispersing agents, stickers, adhesives, and the like, in accordance with agricultural practices. Examples of adjuvants which are commonly used in the art can be found in the John W. McCutcheon, Inc. publication Detergents and Emulsifiers Annual.

The diphenyl ether compounds of this invention can be dissolved in any appropriate solvent. Examples of solvents which are useful, in the practice of this invention include alcohols, ketones aromatic hydrocarbons, halogenated hydrocarbons, 'dimethylfo'rmami de, dioxane, dimethyl sulfoxide, and. the like. Mixtures of these solvents can also be used. The concentration of the solution can vary from about 2% to about 98% with a preferred range being about 25% to about 75%.

For-the preparation of emulsifiable concentrates, the diphenyl ether can be dissolved in organic'solvents, such as benzene, toluene, xylene, methylated naphthalene, corn oil, pine oil, o-dichlorobenzene, isophorone, cyclohexanone, methyl'oleate, and the like, or in mixtures of these solvents, together with an emulsifying agentwhich permits dispersion in water. Suitable emulsifiers include, for example,; the ethylene oxide derivatives of alkylphenols or long-chain alcohols, mercaptans, carboxylic acids, and reactive amines and partially esterified polyvhydric alcohols; Solvent-soluble sulfates or sulfonates, suchas; the alkaline earth salts or amine salts of alkylbenzenesulfonatesand the'fatty alcohol sodium sulfates, having surface-active properties can be used as emulsifiers either alone or in conjunction with an ethylene oxide reaction product. -Flowable emulsion concentrates. are formulated similarly to the emnlsifiable concentrates and include, in addition to the above components, water and astabilizing agent such as a water-soluble cellulose derivative or a water-soluble salt of-a polyacrylic acid. The concentration of the active ingredient in emulsifiable concentrates is usually about 10% to 60% and in fiowable emulsion concentrates,.this can be as high as about 75 J and/or dispersing agents'in such mixtures. The concentration of active ingredients in such formulations is usually in the range of about 20% to 98%, preferably about 40% to 75%. A dispersing agent can constitute about 0.5% to about 3% of the composition, and a wetting agent can constitute from about 0.1% to about-5% of thecor'ripositiom Y Dusts can be prepared by mixing the compounds of the invention with finely divided inert solids which;r r 1 ay be organic or inorganicin'nature. Materials'nseful.for this purpose include, for example, botanical flours, silica's, silicates, carbonates and clays. One convenient method of preparing a dust is to-dilute a wettable powder with a finely divided carrier. Dust concentrates containing about 20% to 80% of the active ingredient are com monlymade and are subsequently diluted to about 1% to use concentration. I, Granular formulations can be prepared by impregnating a solid such as granular fullers e'arth, vermicul ite, ground corn c obs,seed hulls, including bran or other grain-hulls, or similar material. A solution of one or more of the diphenyl ethers in a volatile organic solvent can be sprayed or mixed with the granular solid and'the solvent then removed by evaporation. The granular material can have any suitable size, with a" preferable size range of 16 to 60 mesh. The diphenyl ether will usually comprise about 2 to of the granular formulation. v

The diphenyl ethers of the invention can also be mixed with fertilizers or fertilizing materials before their application. In one'type 'of solid fertilizing composition in which the diphenyl ethers canbe used, particles of [a fertilizer or fertilizing ingredients, such as ammonium sulfate, ammonium nitrate, or ammonium phosphate, can be coated with one or more of the ethers. The solid diphenyl ethers and solid fertilizing material can also be admixed in mixing or blending equipment, or they can be incorporated with fertilizers in granular formulationsiAny relative proportion of diphenyl ether and fertilizer can be used which is suitable for the crops andweeds to be treated. The diphenyl ether will commonly be from about 5% to about of the fertilizing composition. These compositions provide fertilizing. materials which promote the rapid growth of desired plants; and. at the' sarne time control the growth of undesired plants; i The diphenyl ethers of the invention c'an be applie d as herbicidal sprays ,by methods commonly 'femploy' (1 such as conventional high-gallonage hydraulic sprays,lov'v gallonage sprays, airblast spray, aerial sprays and dusts. For low volume applications a solution of the compound isusually used. The dilution and rate of application will usually depend upon such factors as the type of equipment employed, the method of application, the area to be treated and the type andstage of'deve'lopmerit' of the weeds. I For some applications, it may be desirable to add one. or more other herbicides along with diphenyl ethers of the invention. Examples of other herbicides which can be incorporated to provide additional advantages and effectiveness include:

CARBOXYLIC ACIDS AND DERIVATIVES 2,3,6-trichlorobenzoic acid and its salts 2,3,5,6-tetrachlorobenzoic acid and its salts 2-methoxy-3,5,6-trichlorobenzoic acid and its salts 2-methoxy-3,6-dichlorobenzoic acid and its salts 2-methyl-3,6-dichlorobenzoic acid and its salts 2,3-dichloro-6-methylbenzoic acid and its salts 2,4-dichlorophenoxyacetic acid and its salts and esters 65 2,4,S-trichlorophenoxyacetic acid and its salts' and esters Z-methyl-4-chlorophenoxyacetic acidand itssalts and esters 2- (2,4,5 -trichlorophenoxy) propioni esters 4-(2,4-dichlorophenoxy)butyric acid and itssa'ltsl and esters 4-(2-1nethyl-4-chlorophenoxy)butyric acid and and esters 2,3,6-trichlorophenylacetic acid a d-itssalts i l 6 3,6endoxohexahydrophthalic acid dimethyl 2,3,5,6-tetrachloroterephthalate trichloroacetic acid and its salts 2,2-dichloropropionic acid and its salts 2,3-dichloroisobutyric acid and its salts CARBAMIC ACLD DERIVATIVES ethyl N,N-di(n-propyl)thiolcarbamate propyl N,N-di(n-propyl)thiolcarbamate ethyl N-ethyl-N-(n-butyl)thiolcarbamate propyl N-ethyl-N-(n-butyl)thiolcarbamate 2-chloroallyl N,N-diethyldithiocarbamate N-methyldithiocarbamic acid salts ethyl 1-hexamethyleneiminecarbothiolate isopropyl N-phenylcarbamate isopropyl N-(m-chlorophenyl) carbamate 4-chloro-2-butynyl N-(m-chlorophenyl) carbamate methyl N-(3,4-dichlorophenyl) carbamate PHENOLS dinitro-o-(sec-butyl)phenol and its salts pentachlorophenol and its salts VTSUBSTITUTED UREAS SUBSTITUTED TRIAZINES 2-chloro-4,6- =bis(ethylamino)-s-triazine 2l-chloro-4-ethylamino-6-isopropylamino-s-triazine.

" 2-methylmerc apto- 4,6-bis (isopropylamino -s-triazine 2 -methylmercapto-4,,6-bis ethylamino) -s-triazine Z-methylrnercapto-4-ethylamino-6-isopropylamino-svtriazine 1 2-.chl0r0 -4,6-bis (isopropyla-mino -s-triazine 2-methoxy-4,6-bis(ethylamino)-s-triazine- 2-methoxye4 ethylaminq-6-isopropylamino-s-triazine 2 methylmercapto-4-(2-methoxyethylamino)-6-isopropyl- 'ammo-s-triazine DIPHENYL ETHER DERIVATIVES ANILIDES N-(3 chloro-4-methylphenyl)-2-rnethylpentanamide N'(3, l-diclilorbphenyl)trimethylacetamide N-(3,4-di chlorophenyl) -a;u-dimethylvaleramide ,N-isopropyl N pheriylchloroacetamide i N-n-butox'ymethyl-N-(2,6-diethylphenyl) chloroacetamide u N-n-methoxyniethyl-N- (2,6-diethylphenyl) chloroacetamide 7 URACILS -bromo-3-s-butyl-6-methyluracil 5-bromo-3-cyclohexy1-1,6-dimethyluracil 3-cyclohexyl-5,6-trimethyleneuracil 5-bromo-3 -isopropyl-6-methyluracil 3tert-buty1-5-ch1oro-6-methyluracil NITRILES 2,6-dichlorobenzonitrile diphenylacetonitrile 3,S-dibromo-4-hydroxybenzonitrile 3,5 -diiodo-4-hydroxybenzonitrile 1 OTHER ORGANIC HERBICIDES'Z "f 1, 1'-dimethyl-4,4-bipyridinium salts 3,4,5,6-tetrahydro-3,5-dimethyl-2-thio-2H-1,3,5:

thiadiazine. 7 When mixtures of herbicides are employed, the relative proportions which are used will depend upon the crop to be treated and the degree of selectivity in weed control which is desired.

The diphenyl ethers of the invention or their-precursors can be prepared by reacting a suitably substituted phenol, or the potassium or sodium salt of the phenol, with a suitably substituted halobenzene, such as a chloroor fluorobenzene, in the presence of an alkaline agent.

The following examples will further illustrate this'in-- vention but are not intended to limit it in anyway; In Table I, typical diphenyl ethers of the invention are listed, with their melting points and elemental analyses. Specific, illustrative preparations-of the compounds 3 and 7 are described after Table I.

TABLE I.-DIPHENYL of Examples" 6,7-dihydrodipyridol[1,2-a:2',1'-c]pyrazidinium salts Preparation of 2-chloro-a,e,u-trifluoro-ptolyl-3- ethoxy-4-nitrophenyl ether (a) 1,3, bis(2 e chloro-a,a,a-trifluoro-p-tolyloxy)benz'enel-j Aj solution of potassium hydroxide (3.26 g., 0.05 mole, 85%) in water (-3 g.) is added slowly dropwise toa solution of resorcinol (2.75 g., 0.025 mole) and 3,4- dich1oro-a,e,m-tritiuorotoluene (10.75 g., 0.05 mole) in sulfolane (125 ml.) at ISO-160 C., with stirring. When the addition iscomplete, the strongly colored reaction mixture is stirred at ISO-160 C. overnight, then'cooled, diluted With'benzene (200 ml.), and washed cautiously with water (700 ml.). Hexane (200 ml.) is added and the mixture washed with water (600 ml.), dilute sulfuric acid (600 ml.), dilute sodium hydroxide solution (600 ml.), and water (600 ml.), dried, and the solvent removed to give 1,3 bis(2-chloro-a,a,a-trifluoro-p-tolyloxy)benzene (8.6 g., B.P 160-70" C./0.l mm,

(h) f l,3-bis( 2-chloro a,ot,oz-trifiuoro-p-to1yloxy) -4-nitrobenzene'J-l,3-bis(2-chloro-a,a,a-trifluoro p tolyloxy) benzene ('12 g., 0.0255 mole) is' added to a mixture of concentrated nitric acid (12 g.) and sulfuric acid (15 g.) at 5 C. The temperature is then allowed to rise to 2530 C. with manual stirring and mild ice bath cooling and after l020 minutes, the oil solidifies. The mixture'is' taken up in water/benzene (400 ml.)/hexane (400 ml.) and the organic phase is washed with water, dried, filtered through activated silica gel (-20 g.), and the solvents removed. The residue is recrystallized from isopropanol to give l,3-bis(2-chloro-a,a,a-trifiuoro-p-tolyloxy) l-nit lrobenzene (7.4 g., 56%), M.P. ll0-l11.5 C. (c) 2 chloro 0:,0:,a-trifiuOrO-p-tOlYl-3-6LhOXY-4-l1itl'0- phenyl etheh- -A 10% solution of potassium hydroxide in ethanol (10 ml.) is added to a solution of l,3-bis(2- chloro-e, ,e-trifiuoro-p tolyloxy)-4 nitrobenzene (2 g., 0.0039 mole) in dioxane (20 ml.). After forty minutes at room temperature, the solution is heated to 45 C. for eight minutes, then cooled, diluted with benzene (50 ml.) and hexane -(50 ml.) and washed with water 3X 100 ml.), dried, and the solvents removed. The residue is recrystallized from isopropanol to give 2-Chl0l0-a,oz,atrifluoro-p-tolyl-Ii-ethoxy 4 nitrophenylether (1.21 g., 86% M.P. 83-84" C.

, EXAMPLE 7 Preparauba of 2-cyano-a,a,a-trifiuoro-p-tolyl-3-ethoxy-4- i nitrophenyl ether 2 cyano a,e,atrifluoro-p-t0lyl-3-ethoxy-4-nitropheny1 ether.A solution of potassium hydroxide (2.6 g., 0.04

Analysis, percent Found Reqs. M.P. Y Z (C.) 0 H N 01 F C H N C! F H O CaHu 72-75 54. 67 3. 75' 41. 9 'v I 25 55. 05 3. 4. 28 17. 42 H O CH: 95-100 48. 78 2. 89 4. 01 91 48. 33, 2. 01 4. 03 10. 20 16. 40 H O 02H: 83 84 49. 85 3. 33 3. 68 51 49. 80 3. 07 3. 87 9. 80 15.75 H 0 03111-1 49. 5-51 51. 02 3. 58 -3. 52. 58 51. 18 3. 49 3. 73 9. 42 15. 16 H O OBH'PD -76 51. 36 3. 60 3. 62 00 51. 18 3. 49 3. 73 9. 42 15. 16 H O C4Hn-n 51-52 52. 07 4. 03 3. 38v 65 52. 42 3. 88 3. 59 9. 10 14. 63' H OCzHs 143-145 54.84 3. 36' 8101" .85 52.18 3.01 7.61 15.48 H O CaHz-n 96. 5-98 55. 70 3. 65 7. 56 3 55. 74 3. 58 7. 65 15. 56 v H H: 86-88. 5 55. 95 2. 8. 62 68 55. 2. 81 8. 72 17. 69

m91sw 7-3f7z;P re-#1 4;.3r&th9 Y: -It l? ml; 3 2,; 0.04 mole) in methanol (39 n stripped .tqflrypess under reduced pressure. A'residue of potassium 3-etliox3'i- 4-nitrophenoxide is .tiissolvedi in sulfolane (200 g.) and 4-chloro-3-cyanqsbenmtrifluoride; (8,2 g.,,- 0.04 mole) is added. Gas-liquid'chromatograph shows the reaction to be complete-after stirring at l1'( Q." for 4% hours 135 'CfforQMz hours. The=raction migttur'e is cooled and poured finto deionized-1 water and th precipitate "jyvhich formsflisffiltered otr' and-air dried. Recrystallization from isopropanol' yields2-cyano b ak trifiuoro-p-tolyl-ii-etho)ty- 4-nitrophenyl eth e r I t g., M P, l 43 C.

EXAMPLES 10 TO 19 Following the procdures-of' Examples l to 9, other diphenyl ethers; of formula; I are. preparcd sAmong .the

compounds which are prepared by.; these pr ocedures are;

It should be noted that the diphehyl ethers of the inven- 40 tion can also be named correctly using difierent systems uoro-4,6-xylyl-3-ethoxy-4- otE nomenclature. For example, the diphenyl ether of Example 3 can also be named as 2-cyano-4-trifluoromethyl-3'-ethoxy-4'-nitrodiphenyl ether. However, within the specification and claims of this invention the Chemical Abstracts system of nomenclature, as exemplified in Examples 1-19, has been followed.

The following examples show the herbicidal properties of the diphenyl ethers of the invention.

EXAMPLE 20 This example shows the herbicidal activity of diphenyl ethers of the invention towards a number of common weeds. Using the procedure described below, diphenyl ethers were evaluated for control of the following weeds.

At 10 pounds per acre:

Monocots:

Barnyard grass (Echinochloa crusgalli) Crabgrass (Digitaria spp.) Nutsedge (Cyperus esculentus) Wild oats (Avena fatua) Dicots:

Bindweed (Convolvulusarvensis) Curly dock (Rzgmex crirpus) Velvetleaf (Albutilon theophrasti) Wild mustard (Brassica haber) At 2 and 4 pounds per acre:

Monocots:

Barnyard grass (Echinochloa crusgalli) Crabgrass (Digitaria spp.) Downy brome (Bromus tectorum) Foxtail (Selaria faberii) Johnson grass (Sorghum halepense) Nutsedge (Cyperus escujentus) Quackgrass (Agropyron repens) 10 Ryegrass (Lolium perenne) Wild oats (Avena fatua) Yellow millet'GP nicum miliaceum) Dicotsz I, Bindweed (Convolvulus arvensis) Cocklebur (Xanthizpn pensylvanicum) Curly dock (Rumex crispus) I Lambs-quarters (Chenopodium album) N Morning glory (lpomoea purpurea) Pigweed (Amaramhus retroflexus) *Smar'twced (Polygonum pensylvanicum) Velvetleaf (Abutilon theophrasti) .Wild carrot (Daucus carota) Wild mustard (Brassica haber).

Thefollowingtest 'procedure is employed: Seeds of selected crops and weeds are planted in soil' in flats. For preeniergence tests, the flats are treated with the test compound immediately after the planting. For postemergence tests, the seeds are allowed to germinate, and after two weeks the flats are treated wth the test compound. The compound to be evaluated in dissolved in acetone, diluted with water, and sprayed over the flats using a carrier volume equivalent to 50 gallons per acre at the rate of application (pounds per acre, lb./a.) specified in the tables. About two weeks after the application of the test compound, the state of growth of the plants is observed and the phytotoxic efiect of the compound is evaluated. Table II gives the average percent control achieved by the test compounds in terms of the percent of the plants which are killed by the compounds.

TABLE IL-HERBICIDAL ACTIVITY NorE.-M=Monocots; D=Dieots.

It is to be understood that changes and variations may be made without departing from the spirit and scope of the invention as defined by the appended claims.

What is claimed is:

1. A compound of the formula wherein halogen atom and Xis'a halogen atom; a tri'fluororne't-hyl X is a hydrogen atom, a halogen atom, 'a trifluoro- 'gf0up;o'r'a (C -C alkylgroup. l

methyl group, or a (C -C alkyl group', I i 7 5 Y is a hydrogen atom, a halogen atom, ora trifiuoro- "1 Q in Cited methyl group, and 5 I UNITED STATES PATENTS Z is (C146) alkoXY gYOuP, (C1-C4) alkyl gmup: 3,080,225 Q3/i963 Wilson et mono-26mm R X a halogen atom- .;3 ,-3=22,s2s V 5/19 7 Martin et al. 260+612-R X 2. A compound according to claim 1 wherein Y is a --3, 4 2Q8)92 ?H 1959 tMartmJct 1 .,2' +5f1 3.R hydrogen atom. 3,454,;92, 7/1969- Kato et ah 260%61211 A amid-i118 wherein X is a 3,647 888. 3/19723-1Rohr1'et a. chlorine atom.

4. A compound according to claim 2 wherein Z is an BERNARD LY N; mar iE m i alkoxy group. I 5. A compound according to claim 4 wherein Z is an '15 I a-Q -X ethoxy group and X is a chlorine atom. 1 Q; In -1'9 1 ,'-124;;.260 -6l3 R 465 1 465 G,'-609 571', -6. A compound according to claim; l-wherein Y- -isla 520,473 1 UNITED STATES PATENT AND TRADEMARK OFFICE Certificate Patent No. 3,798,276 Patented March 19, 1974 Horst O. Bayer, Colin Swithenbank and Roy Y. Yih

Application having been made by Horst O. Bayer, Colin Swithenbank, and Roy Y. Yih, the inventors named in the patent above identified, and Rohm and Haas Co., the assignees, for the issuance of a certificate under the provisions of Title 35, Section 256, of the United States Code, deleting the name of Roy Y. Yih as a joint inventor, and a showing and proof of facts satisfying the requirements of the said section having been submitted, it is this 28th day of Feb. 1984, certified that the name of the said Roy Y. Yih is hereby deleted from the said patent as a joint inventor with the said Horst O. Bayer and Colin Swithenbank.

Fred W. Sherling, Associate Solicitor.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,798,276 Dated March 19., 197% Inventor(s) Horst O. Bayer, Colin Swithenbank, and Roy Y. Yih

hove-identified patent It is certified that error appears in the a wn below:

and that said Letters Patent are hereby corrected as sho In the first column of the patent, after identification of the inventors and before the line reading No drawing.", insert Assignee: Rohm and Haas Company, Philadelphia,

Pennsylvania.

Signed and sealed this 16th day of July 1971+.

(SEAL) Attest:

McCOY M. GIBSON, JR. C. MARSHALL DANN Commissioner of Patents Attesting Officer 

